EP0672212B1 - Use of hydrolysed copolymers of n-vinyl carboxylic acid amides and monoethylenically unsaturated carboxylic acids in the manufacture of paper - Google Patents

Use of hydrolysed copolymers of n-vinyl carboxylic acid amides and monoethylenically unsaturated carboxylic acids in the manufacture of paper Download PDF

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Publication number
EP0672212B1
EP0672212B1 EP94901873A EP94901873A EP0672212B1 EP 0672212 B1 EP0672212 B1 EP 0672212B1 EP 94901873 A EP94901873 A EP 94901873A EP 94901873 A EP94901873 A EP 94901873A EP 0672212 B1 EP0672212 B1 EP 0672212B1
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mol
paper
copolymer
copolymers
acid
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German (de)
French (fr)
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EP0672212A1 (en
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Claudia Nilz
Walter Denzinger
Heinrich Hartmann
Michael Kroener
Friedrich Linhart
Rudolf Schuhmacher
Dietmar Moench
Andreas Stange
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

  • the invention relates to the use of copolymers which salt by copolymerizing N-vinylcarboxamides with monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and / or their alkali metal, alkaline earth metal or ammonium and optionally vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or Their mixtures and optionally compounds which have at least two ethylenically unsaturated non-conjugated double bonds in the molecule, and partial or complete removal of the groups from the N-vinylcarboxamides polymerized into the copolyacyl merisate to form amine or ammonium groups, are available as additives to the paper stock to increase the drainage rate and the retention in the paper production as well as the dry and wet strength of the paper.
  • EP-A-0 216 387 discloses water-soluble copolymers containing vinylamine units which are obtained by copolymerizing N-vinylformamide with monoethylenically unsaturated monomers from the group consisting of vinyl acetate, vinyl propionate, C 1 - to C 4 -alkyl vinyl ether, the esters, nitriles and amides of Acrylic acid and methacrylic acid and N-vinylpyrrolidone and cleavage of the formyl groups from the copolymers are available.
  • These copolymers and preferably copolymers of N-vinylformamide and vinyl acetate, the monomer units of which are each hydrolyzed to 30 to 100 mol%, are used as agents for increasing the dry and wet strength of paper.
  • Copolymers are known from EP-A-0 251 182 which contain vinylamine groups in salt form, vinylformamide and acrylonitrile groups and, if appropriate, acrylamide and acrylic acid groups.
  • the proportion of polymerized acrylic acid or methacrylic acid is at most 6.4 mol%.
  • the present invention is based on the object of providing a further paper auxiliary which, when added to the paper stock, leads to an increase in the mechanical strength of the papers produced in this way and at the same time causes an increase in dewatering acceleration and retention.
  • copolymers to be used according to the invention are prepared by free-radically initiated copolymerization of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids, preferably acrylic acid and / or methacrylic acid and their salts and optionally other monoethylenically unsaturated monomers.
  • the copolymerization can optionally also be carried out in the presence of crosslinking agents.
  • Suitable monomers are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide.
  • the monomers mentioned can be used either alone or as a mixture with one another to prepare the copolymers. From this group of monomers, preference is given to using N-vinylformamide.
  • the copolymers contain the monomers of group a) in amounts of 5 to 99, preferably 30 to 95 mol% in copolymerized form.
  • Monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts of these monomers are suitable as monomers of group b).
  • This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, maleic acid or else mixtures of the carboxylic acids mentioned, in particular mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid.
  • the monomers of group b) can either be in the form of the free carboxylic acids or in part or fully neutralized form can be used in the copolymerization.
  • the neutralization of the monoethylenically unsaturated carboxylic acids use is made, for example, of alkali metal, alkaline earth metal bases, ammonia or amines, for example sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, ethanolamine, diethanolamine, triethanolethylene triethanolethylene, morphamine, diethylamine, morphamine .
  • the copolymers contain the monomers of group b) in an amount of 95 to 1, preferably 70 to 5 mol% in copolymerized form.
  • copolymers of the monomers a) and b) can, if appropriate, be modified by using vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or mixtures thereof in the copolymerization. If the monomers of group c) for Modification of the copolymers are used, they are present in amounts of up to 30 mol% in the copolymers in copolymerized form, preferably in amounts of 1 to 20 mol%.
  • copolymers of the monomers a) and b) and, if appropriate, c) can further be modified by carrying out the copolymerization in the presence of monomers of group d), which are compounds which contain at least two ethylenically unsaturated, non-conjugated double bonds have in the molecule.
  • monomers of group d) which are compounds which contain at least two ethylenically unsaturated, non-conjugated double bonds have in the molecule.
  • the use of the monomers of group d) in the copolymerization causes an increase in the K values of the copolymers.
  • Suitable compounds of group d) are, for example, methylenebisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, such as glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and at least twofold esterified with acrylic acid or methacrylic acid or polyethylene glycols, such as pentaerythritol and glucose.
  • Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose.
  • water-soluble monomers such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight of up to 3,000. If the monomers of group d) are used to modify the copolymers, the amounts used are up to 2 mol%. If they are used, they are preferably present in the copolymers in copolymerized form in an amount of from 0.01 to 1 mol%.
  • the copolymers are prepared by known processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds which form free radicals under the polymerization conditions.
  • the polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C.
  • Suitable initiators are, for example, azo and peroxy compounds and the usual redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. These systems can optionally also contain small amounts of a heavy metal salt.
  • the copolymers are preferably prepared by solution polymerization in water, the monomers of group b) preferably being used in the salt form and the pH being kept between 6 and 8 during the polymerization.
  • a buffer such as, for example, disodium hydrogen phosphate.
  • Water-soluble azo compounds such as 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (2- methyl-N-phenylpropionamidine) dihydrochloride used.
  • the copolymerization is carried out in the presence of a regulator.
  • Suitable regulators are, for example, secondary alcohols, such as isopropanol and sec-butanol, hydroxylamine, formic acid, and mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, thioglycolic acid, thiolactic acid, tert-butyl mercaptan, octyl mercaptan and dodecyl mercaptan.
  • the regulators are usually used in amounts of 0.01 to 5% by weight, based on the monomers used. If secondary alcohols are used as regulators, the polymerization can also take place in the presence of substantially larger amounts, for example in amounts up to 80% by weight, based on the monomers. In these cases, the secondary alcohols are also solvents for the monomers.
  • the copolymers thus obtainable have K values of 30 to 300, preferably 50 to 250.
  • the K values are determined according to H. Fikentscher in 5% aqueous saline solution at pH 7, 25 ° C. and a polymer concentration of 0.1% by weight. -%.
  • hydrolyzed copolymers to be used according to the invention are obtained from the copolymers described above by partially or completely splitting off the formyl groups from the monomer I copolymerized into the copolymer with formation of amine or ammonium groups:
  • copolymers contain, in addition to the monomers a) and b), copolymerized monomers of group c), the copolymerized monomers c) can also be chemically changed depending on the hydrolysis condition chosen, for example vinyl alcohol units are formed from vinyl acetate units.
  • the degree of hydrolysis of the units II specified above is preferably 60 to 95%.
  • Hydrolysis of the copolymers in aqueous solution or suspension at reaction temperatures of 20 to 100 ° C. has proven particularly useful. If the unhydrolyzed copolymers are sparingly soluble in water, they usually dissolve in the reaction medium as hydrolysis proceeds. Following an acidic hydrolysis, the reaction mixture is optionally neutralized with bases, preferably sodium hydroxide solution. If the hydrolysis has been carried out with bases, the reaction mixture can, if appropriate, be neutralized by adding acids, preferably hydrochloric acid.
  • the pH values of the reaction mixture can be between 1 and 10, preferably between 3 and 8, after the hydrolysis. Depending on the composition, the hydrolyzed copolymers can be sparingly soluble in certain pH ranges.
  • the K value of the hydrolyzed copolymers is 10 to 300, preferably 15 to 200 (measured in 5% aqueous sodium chloride solution at a polymer concentration of 0.1% by weight, a pH of 1.5 and a temperature of 25 ° C).
  • the K values of the copolymers were determined according to H. Fikentscher, Cellulosechemie, Vol. 13, 48-64 and 71-74 (1932) in 5% aqueous saline solution at 25 ° C and a polymer concentration of 0.1% by weight. wherein the K value of the non-hydrolyzed copolymers was measured at pH 7 and that of the hydrolyzed copolymers at 1.5.
  • a polymerization apparatus 965.3 g of water, 1.34 g of a 75% aqueous phosphoric acid and 0.92 g of a 50% aqueous sodium hydroxide solution are heated to a temperature of 70 ° C. in a stream of nitrogen. As soon as this temperature has been reached, a mixture of 100 g of water, 60 g of acrylic acid and 66.5 g of 50% strength aqueous sodium hydroxide solution and, separately therefrom, 141.4 g of N-vinylformamide and likewise separately of it are added in each case within 2 hours Evenly add 0.05 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride in 25 g of water.
  • the degree of hydrolysis of the polymerized N-vinylformamide is 95%.
  • the reaction solution has a polymer content of 5.6%.
  • the copolymer contains vinylamine hydrochloride, vinylformamide and acrylic acid units (hydrolyzed copolymer 2).
  • the K value of the polymer is 126.
  • a 0.5% pulp suspension in water was made from 50% spruce sulfite pulp and 50% beech sulfite pulp.
  • the pH of the stock suspension was 7.0 and the freeness was 30 ° Schopper-Riegler (SR).
  • the stock suspension was then divided into 5 equal parts, of which 4 of the stock suspensions were mixed with the additives indicated under b) to e).
  • the 5 stock suspensions were then processed into sheets with a basis weight of 80 g / m 2 in a Rapid-Köthen laboratory sheet former.
  • Samples b) to j) were each dewatered after a 5-minute exposure time of the additive in a laboratory sheet former to form sheets with a mass per unit area of 68 g / m 2 .
  • the sheets were burned in a muffle furnace at temperatures of 900 to 1000 ° C and the residue on ignition was determined gravimetrically. The results obtained are shown in Table 3.

Abstract

Described is the use, as additives to paper-making pulp, of copolymers obtained by polymerizing a) 5 to 99 mole % of N-vinyl carboxylic acid amides, b) 95 to 1 mole % of monoethylenically unsaturated carboxylic acids and/or alkali-metal, alkaline-earth metal, ammonium or amine salts thereof, and optionally c) up to 30 mole % of other monoethylenically unsaturated compounds, and optionally d) up to 2 mole % of crosslinking agents, and subsequently splitting off some or all of the formyl groups from the N-vinyl carboxylic acid amide units in the copolymer to form amine or ammonium groups. Such additives increase the water-removal speed and retention during the manufacture of paper, as well as the dry and wet strength of the paper.

Description

Die Erfindung betrifft die Verwendung von Copolymerisaten, die durch Copolymerisieren von N-Vinylcarbonsäureamiden mit monoethylenisch ungesättigten Carbonsäuren mit 3 bis 8 C-Atomen und/oder deren Alkalimetall-, Erdalkalimettall oder Ammonium salzen und ggf. Vinylacetat, N-Vinylpyrrolidon, N-Vinylimidazol oder deren Mischungen und ggf. Verbindungen, die mindestens zwei ethylenisch ungesättigte nicht konjugierte Doppelbindungen im Molekül aufweisen, und teilweise oder vollständige Abspaltung der gruppen aus dem in das Copoly-Acylmerisat einpolymerisierten N-Vinylcarbonsäureamiden unter Bildung von Amin- bzw. Ammoniumgruppen erhältlich sind, als Zusatz zum Papierstoff zur Erhöhung der Entwässerungsgeschwindigkeit und der Retention bei der Papierherstellung sowie der Trocken- und Naßfestigkeit des Papiers.The invention relates to the use of copolymers which salt by copolymerizing N-vinylcarboxamides with monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and / or their alkali metal, alkaline earth metal or ammonium and optionally vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or Their mixtures and optionally compounds which have at least two ethylenically unsaturated non-conjugated double bonds in the molecule, and partial or complete removal of the groups from the N-vinylcarboxamides polymerized into the copolyacyl merisate to form amine or ammonium groups, are available as additives to the paper stock to increase the drainage rate and the retention in the paper production as well as the dry and wet strength of the paper.

Aus der US-A-2 721 140 ist bekannt, Polyvinylaminhydrochlorid als Hilfsmittel bei der Herstellung von Papier zu verwenden, wobei man insbesondere Papiere mit hoher Naßfestigkeit erhält. Das so behandelte Papier besitzt jedoch eine relativ hohe Vergilbungsneigung.From US-A-2 721 140 it is known to use polyvinylamine hydrochloride as an aid in the production of paper, in particular papers with high wet strength being obtained. However, the paper treated in this way has a relatively high tendency to yellowing.

Aus der US-A-4 421 602 sind partiell hydrolysierte, wasserlösliche Homopolymerisate des N-Vinylformamids bekannt, die N-Vinylformamid- und Vinylamin-Einheiten enthalten. Diese Polymerisate werden als Mittel zur Erhöhung der Flockung, Retention und Entwässerungsgeschwindigkeit bei der Herstellung von Papier verwendet.From US-A-4 421 602 partially hydrolyzed, water-soluble homopolymers of N-vinylformamide are known which contain N-vinylformamide and vinylamine units. These polymers are used as agents to increase flocculation, retention and drainage speed in the manufacture of paper.

Aus der EP-A-0 438 744 sind Copolymerisate bekannt, die 99 bis 50 Gew.-% mindestens einer monoethylenisch ungesättigten Carbonsäure mit 3 bis 8 C-Atomen oder deren Salzen und 1 bis 50 Gew.-% N-Vinylcarbonsäureamide, vorzugsweise N-Vinylformamid, einpolymerisiert enthalten und die einer Hydrolyse unterworfen worden sind, bei der die Formylgruppen der N-Vinylcarbonsäureamide unter Bildung von Amin- bzw. Ammoniumgruppen abgespalten sind. Diese Copolymerisate werden als Wasserbehandlungsmittel zur Verminderung der Kesselsteinabscheidung und der Wasserhärteausscheidung in wasserführenden Systemen und bei der Eindampfung von Zuckersaft verwendet.Copolymers are known from EP-A-0 438 744 which contain 99 to 50% by weight of at least one monoethylenically unsaturated carboxylic acid with 3 to 8 C atoms or salts thereof and 1 to 50% by weight of N-vinylcarboxamides, preferably N. -Vinylformamid, contained in copolymerized form and which have been subjected to hydrolysis, in which the formyl groups of the N-vinylcarboxamides are split off to form amine or ammonium groups. These copolymers are used as water treatment agents to reduce scale deposition and water hardness excretion in water-bearing systems and in the evaporation of sugar juice.

Aus der EP-A-0 216 387 sind Vinylamineinheiten enthaltende wasserlösliche Copolymerisate bekannt, die durch Copolymerisieren von N-Vinylformamid mit monoethylenisch ungesättigten Monomeren aus der Gruppe Vinylacetat, Vinylpropionat, C1- bis C4-Alkylvinylether, der Ester, Nitrile und Amide von Acrylsäure und Methacrylsäure und N-Vinylpyrrolidon und Abspalten der Formylgruppen aus den Copolymerisaten erhältlich sind. Diese Copolymerisate und vorzugsweise Copolymerisate aus N-Vinylformamid und Vinylacetat, deren Monomereinheiten zu jeweils 30 bis 100 Mol-% hydrolysiert sind, werden als Mittel zur Erhöhung der Trocken- und Naßfestigkeit von Papier verwendet.EP-A-0 216 387 discloses water-soluble copolymers containing vinylamine units which are obtained by copolymerizing N-vinylformamide with monoethylenically unsaturated monomers from the group consisting of vinyl acetate, vinyl propionate, C 1 - to C 4 -alkyl vinyl ether, the esters, nitriles and amides of Acrylic acid and methacrylic acid and N-vinylpyrrolidone and cleavage of the formyl groups from the copolymers are available. These copolymers and preferably copolymers of N-vinylformamide and vinyl acetate, the monomer units of which are each hydrolyzed to 30 to 100 mol%, are used as agents for increasing the dry and wet strength of paper.

Aus der EP-A-0 251 182 sind Copolymerisate bekannt, die Vinylamin-Gruppen in Salzform, Vinylformamid- und Acrylnitrilgruppen sowie ggfs. Acrylamid- und Acrylsäuregruppen enthalten. Der Anteil an einpolymerisierter Acrylsaure bzw. Methacrylsäure beträgt höchstens 6,4 Mol-%. Diese Copolymerisate werden bei der Herstellung von Papier verwendet und wirken als Entwasserungsund Retentionsmittel sowie als Mittel zur Erhöhung der Trockenfestigkeit von Papier.Copolymers are known from EP-A-0 251 182 which contain vinylamine groups in salt form, vinylformamide and acrylonitrile groups and, if appropriate, acrylamide and acrylic acid groups. The proportion of polymerized acrylic acid or methacrylic acid is at most 6.4 mol%. These copolymers are used in the manufacture of paper and act as dewatering and retention agents and as an agent for increasing the dry strength of paper.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein weiteres Papierhilfsmittel zur Verfügung zu stellen, das beim Zusatz zum Papierstoff zu einer Erhöhung der mechanischen Festigkeiten der so hergestellten Papiere führt und gleichzeitig eine Erhöhung der Entwässerungsbeschleunigung und Retention bewirkt.The present invention is based on the object of providing a further paper auxiliary which, when added to the paper stock, leads to an increase in the mechanical strength of the papers produced in this way and at the same time causes an increase in dewatering acceleration and retention.

Die Aufgabe wird erfindungsgemäß gelost mit der Verwendung von Copolymerisaten, die durch Copolymerisieren von

  • a) 5 bis 99 Mol-% N-Vinylcarbonsäureamiden der Formel
    Figure imgb0001
     in der R1, R2 = H oder C1 bis C6-Alkyl bedeuten,
  • b) 95 bis 1-Mol-% monoethylenisch ungesättigten Carbonsäuren mit 3 bis 8 C-Atomen und/oder deren Alkalimetall- und Ammoniumsalzen und gegebenenfalls
  • c) bis zu 30 Mol-% Vinylacetat, N-Vinylpyrrolidon, N-Vinylimidazol oder deren Mischungen und gegebenenfalls
  • d) bis zu 2 Mol-% an Verbindungen, die mindestens zwei ethylenisch ungesättigte nicht-konjugierte Doppelbindungen im Molekul aufweisen
und anschließende teilweise oder vollstandige Abspaltung der Gruppen
Figure imgb0002
 aus den in das Copolymerisat einpolymerisierten Monomeren I unter Bildung von Amin- bzw. Ammoniumgruppen erhältlich sind, als Zusatz zum Papierstoff zur Erhöhung der Entwässerungsgeschwindigkeit und der Retention bei der Papierherstellung sowie der Trocken- und Naßfestigkeit des Papiers.The object is achieved according to the invention with the use of copolymers which are obtained by copolymerizing
  • a) 5 to 99 mol% of N-vinylcarboxamides of the formula
    Figure imgb0001
     in which R 1 , R 2 = H or C 1 to C 6 alkyl,
  • b) 95 to 1 mol% of monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and / or their alkali metal and ammonium salts and, if appropriate
  • c) up to 30 mol% of vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or mixtures thereof and optionally
  • d) up to 2 mol% of compounds which have at least two ethylenically unsaturated non-conjugated double bonds in the molecule
and subsequent partial or complete separation of the groups
Figure imgb0002
 can be obtained from the monomers I polymerized into the copolymer with the formation of amine or ammonium groups, as an additive to the paper stock to increase the drainage rate and retention in paper manufacture, and the dry and wet strength of the paper.

Die erfindungsgemäß zu verwendenden Copolymerisate werden durch radikalisch initiierte Copolymerisation von N-Vinylcarbonsäureamiden und monoethylenisch ungesättigten Carbonsäuren, vorzugsweise Acrylsäure und/oder Methacrylsäure und deren Salzen und gegebenenfalls anderen monoethylenisch ungesättigten Monomeren, hergestellt. Die Copolymerisation kann gegebenenfalls auch zusatzlich noch in Gegenwart von Vernetzern durchgeführt werden.The copolymers to be used according to the invention are prepared by free-radically initiated copolymerization of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids, preferably acrylic acid and / or methacrylic acid and their salts and optionally other monoethylenically unsaturated monomers. The copolymerization can optionally also be carried out in the presence of crosslinking agents.

Als Monomere der Gruppe a) kommen N-Vinylcarbonsäureamide der Formel

Figure imgb0003
in der R1, R2 = H oder C1 bis C6-Alkyl bedeuten, in Betracht. Geeignete Monomere sind beispielsweise N-Vinylformamid, N-Vinyl-N-Methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid, N-Vinyl-N-methylpropionamid und N-Vinylpropionamid. Zur Herstellung der Copolymeren können die genannten Monomeren entweder allein oder in Mischung untereinander eingesetzt werden. Vorzugsweise verwendet man aus dieser Gruppe von Monomeren N-Vinylformamid. Die Copolymerisate enthalten die Monomeren der Gruppe a) in Mengen von 5 bis 99, vorzugsweise 30 bis 95 Mol-% in einpolymerisierter Form.The monomers of group a) are N-vinylcarboxamides of the formula
Figure imgb0003
 in which R 1 , R 2 = H or C 1 to C 6 alkyl, into consideration. Suitable monomers are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide. The monomers mentioned can be used either alone or as a mixture with one another to prepare the copolymers. From this group of monomers, preference is given to using N-vinylformamide. The copolymers contain the monomers of group a) in amounts of 5 to 99, preferably 30 to 95 mol% in copolymerized form.

Als Monomere der Gruppe b) kommen monoethylenisch ungesättigte Carbonsäuren mit 3 bis 8 C-Atomen sowie die wasserlöslichen Salze dieser Monomeren in Betracht. Zu dieser Gruppe von Monomeren gehören beispielsweise Acrylsäure, Methacrylsäure, Dimethylacrylsäure, Ethacrylsäure, Maleinsäure, Citraconsäure, Methylenmalonsäure, Allylessigsäure, Vinylessigsäure, Crotonsäure, Fumarsäure, Mesaconsäure und Itaconsäure. Aus dieser Gruppe von Monomeren verwendet man vorzugsweise Acrylsäure, Methacrylsäure, Maleinsäure oder auch Mischungen der genannten Carbonsäuren, insbesondere Mischungen aus Acrylsäure und Maleinsäure oder Mischungen aus Acrylsäure und Methacrylsäure. Die Monomeren der Gruppe b) können entweder in Form der freien Carbonsäuren oder in partiell oder vollständig neutralisierter Form bei der Copolymerisation eingesetzt werden. Zur Neutralisation der monoethylenisch ungesättigten Carbonsäuren verwendet man beispielsweise Alkalimetall-, Erdalkalimetallbasen, Ammoniak oder Amine, z.B. Natronlauge, Kalilauge, Soda, Pottasche, Natriumhydrogencarbonat, Magnesiumoxid, Calciumhydroxid, Calciumoxid, Ammoniak, Triethylamin, Ethanolamin, Diethanolamin, Triethanolamin, Morpholin, Diethylentriamin oder Tetraethylenpentamin. Die Copolymerisate enthalten die Monomoren der Gruppe b) in einer Menge von 95 bis 1, vorzugsweise 70 bis 5 Mol-% in einpolymerisierter Form.Monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts of these monomers are suitable as monomers of group b). This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, maleic acid or else mixtures of the carboxylic acids mentioned, in particular mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid. The monomers of group b) can either be in the form of the free carboxylic acids or in part or fully neutralized form can be used in the copolymerization. For the neutralization of the monoethylenically unsaturated carboxylic acids, use is made, for example, of alkali metal, alkaline earth metal bases, ammonia or amines, for example sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, ethanolamine, diethanolamine, triethanolethylene triethanolethylene, morphamine, diethylamine, morphamine . The copolymers contain the monomers of group b) in an amount of 95 to 1, preferably 70 to 5 mol% in copolymerized form.

Die Copolymerisate aus den Monomeren a) und b) können ggfs. dadurch modifiziert werden, daß man bei der Copolymerisation Vinylacetat, N-Vinylpyrrolidon, N-Vinylimidazol oder deren Mischungen einsetzt. Sofern die Monomeren der Gruppe c) zur Modifizierung der Copolymerisate eingesetzt werden, sind sie in Mengen bis zu 30 Mol-% in den Copolymerisaten in einpolymerisierter Form vorhanden, vorzugsweise in Mengen von 1 bis 20 Mol-%.The copolymers of the monomers a) and b) can, if appropriate, be modified by using vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or mixtures thereof in the copolymerization. If the monomers of group c) for Modification of the copolymers are used, they are present in amounts of up to 30 mol% in the copolymers in copolymerized form, preferably in amounts of 1 to 20 mol%.

Die Copolymerisate aus den Monomeren a) und b) sowie gegebenenfalls c) können weiterhin dadurch modifiziert werden, daß man die Copolymerisation in Gegenwart von Monomeren der Gruppe d) vornimmt, bei der es sich um Verbindungen handelt, die mindestens zwei ethylenisch ungesättigte nicht konjugierte Doppelbindungen im Molekül aufweisen. Die Mitverwendung der Monomeren der Gruppe d) bei der Copolymerisation bewirkt eine Erhöhung der K-Werte der Copolymerisate. Geeignete Verbindungen der Gruppe d) sind beispielsweise Methylenbisacrylamid, Ester von Acrylsäure und Methacrylsäure mit mehrwertigen Alkoholen, wie Glykoldiacrylat, Glycerintriacrylat, Glycoldimethacrylat, Glycerintrimethacrylat sowie mindestens zweifach mit Acrylsäure oder Methacrylsäure veresterte Polyethylenglykole oder Polyole, wie Pentaerythrit und Glucose. Geeignete Vernetzer sind außerdem Divinylbenzol, Divinyldioxan, Pentaerythrittriallylether und Pentaallylsucrose. Vorzugsweise verwendet man aus dieser Gruppe von Verbindungen wasserlösliche Monomere, wie Glykoldiacrylat oder Glykoldiacrylate von Polyethylenglykolen eines Molekulargewichts bis zu 3.000. Sofern die Monomeren der Gruppe d) zur Modifizierung der Copolymerisate eingesetzt werden, betragen die angewendeten Mengen bis zu 2 Mol-%. Im Falle ihres Einsatzes sind sie vorzugsweise zu 0,01 bis 1 Mol-% in den Copolymerisaten in einpolymerisierter Form enthalten.The copolymers of the monomers a) and b) and, if appropriate, c) can further be modified by carrying out the copolymerization in the presence of monomers of group d), which are compounds which contain at least two ethylenically unsaturated, non-conjugated double bonds have in the molecule. The use of the monomers of group d) in the copolymerization causes an increase in the K values of the copolymers. Suitable compounds of group d) are, for example, methylenebisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, such as glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and at least twofold esterified with acrylic acid or methacrylic acid or polyethylene glycols, such as pentaerythritol and glucose. Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, preference is given to using water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight of up to 3,000. If the monomers of group d) are used to modify the copolymers, the amounts used are up to 2 mol%. If they are used, they are preferably present in the copolymers in copolymerized form in an amount of from 0.01 to 1 mol%.

Bevorzugt ist die Verwendung von Verbindugen, die durch Copolymerisieren von

  • a) 30 bis 95 Mol-% N-Vinylformamid,
  • b) 70 bis 5 Mol-% Acrylsäure, Methacrylsäure und/oder deren Alkalimetall-, Erdalkalimetall-, Ammonium- oder Aminsalzen und
  • c) 0 bis 30 Mol-%, Vinylacetat, N-Vinylpyrrolidon, N-Vinylimidazol oder deren Mischungen und anschließende partielle oder vollständige Hydrolyse der einpolymerisierten N-Vinylformamideinheiten erhältlich sind, z.B. Copolymerisate aus N-Vinylformamid, Acrylsäure und Vinylacetat, Copolymerisate aus N-Vinylformamid, Acrylsäure und N-Vinylpyrrolidon. In den zuletzt beschriebenen Copolymerisaten kann die Acrylsäure ganz oder teilweise durch Methacrylsäure ersetzt sein. Acrylsäure oder Methacrylsäure können partiell oder vollständig mit Natronlauge, Kalilauge, Calciumhydroxid oder Ammoniak neutralisiert sein.
It is preferred to use compounds which are obtained by copolymerizing
  • a) 30 to 95 mol% of N-vinylformamide,
  • b) 70 to 5 mol% of acrylic acid, methacrylic acid and / or their alkali metal, alkaline earth metal, ammonium or amine salts and
  • c) 0 to 30 mol%, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or mixtures thereof and subsequent partial or complete hydrolysis of the polymerized N-vinylformamide units are available, for example copolymers of N-vinylformamide, acrylic acid and vinyl acetate, copolymers of N- Vinyl formamide, acrylic acid and N-vinyl pyrrolidone. In the copolymers described last, acrylic acid completely or partially replaced by methacrylic acid. Acrylic acid or methacrylic acid can be partially or completely neutralized with sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide or ammonia.

Die Herstellung der Copolymerisate erfolgt nach bekannten Verfahren, z.B. der Lösungs-, Fällungs-, Suspensions- oder Emulsionspolymerisation unter Verwendung von Verbindungen, die unter den Polymerisationsbedingungen Radikale bilden. Die Polymerisationstemperaturen liegen üblicherweise in dem Bereich von 30 bis 200, vorzugsweise 40 bis 110°C. Geeignete Initiatoren sind beispielsweise Azo- und Peroxyverbindungen sowie die üblichen Redoxinitiatorsysteme, wie Kombinationen aus Wasserstoffperoxyd und reduzierend wirkenden Verbindungen, z.B. Natriumsulfit, Natriumbisulfit, Natriumformaldehydsulfoxilat und Hydrazin. Diese Systeme können gegebenenfalls zusätzlich noch geringe Mengen eines Schwermetallsalzes enthalten.The copolymers are prepared by known processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds which form free radicals under the polymerization conditions. The polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C. Suitable initiators are, for example, azo and peroxy compounds and the usual redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. These systems can optionally also contain small amounts of a heavy metal salt.

Die Copolymerisate werden bevorzugt durch Lösungspolymerisation in Wasser hergestellt, wobei man die Monomeren der Gruppe b) vorzugsweise in der Salzform einsetzt und den pH-Wert während der Polymerisation zwischen 6 und 8 hält. Um den pH-Wert während der Copolymerisation konstant zu halten, ist es zweckmäßig, geringe Mengen, z.B. 0,5 bis 2 Gew.-%, eines Puffers, wie beispielsweise Dinatriumhydrogenphosphat zuzusetzen. Als Polymerisationsinitiator werden vorzugsweise wasserlösliche Azoverbindungen, wie 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid, 2,2'-Azobis-(4-Methoxy-2,4-dimethylvaleronitril) und 2,2'-Azobis-(2-methyl-N-phenylpropionamidin)dihydrochlorid verwendet.The copolymers are preferably prepared by solution polymerization in water, the monomers of group b) preferably being used in the salt form and the pH being kept between 6 and 8 during the polymerization. In order to keep the pH constant during the copolymerization, it is advisable to use small amounts, e.g. 0.5 to 2% by weight of a buffer, such as, for example, disodium hydrogen phosphate. Water-soluble azo compounds such as 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (2- methyl-N-phenylpropionamidine) dihydrochloride used.

Um niedrigmolekulare Copolymerisate herzustellen, führt man die Copolymerisation in Gegenwart eines Reglers durch. Geeignete Regler sind beispielsweise sekundäre Akohole, wie Isopropanol und sek.-Butanol, Hydroxylamin, Ameisensäure sowie Mercaptoverbindungen, wie Mercaptoethanol, Mercaptopropanol, Mercaptobutanol, Thioglykolsäure, Thiomilchsäure, tert.-Butylmercaptan, Octylmercaptan und Dodecylmercaptan. Die Regler werden üblicherweise in Mengen von 0,01 bis 5 Gew.-%, bezogen auf die eingesetzten Monomeren, angewendet. Sofern man sekundäre Alkohole als Regler verwendet, kann die Polymerisation auch in Gegenwart wesentlich größerer Mengen erfolgen, z.B. in Mengen bis zu 80 Gew.-%, bezogen auf die Monomeren. In diesen Fällen sind die sekundären Alkohole gleichzeitig Lösemittel für die Monomeren.To produce low molecular weight copolymers, the copolymerization is carried out in the presence of a regulator. Suitable regulators are, for example, secondary alcohols, such as isopropanol and sec-butanol, hydroxylamine, formic acid, and mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, thioglycolic acid, thiolactic acid, tert-butyl mercaptan, octyl mercaptan and dodecyl mercaptan. The regulators are usually used in amounts of 0.01 to 5% by weight, based on the monomers used. If secondary alcohols are used as regulators, the polymerization can also take place in the presence of substantially larger amounts, for example in amounts up to 80% by weight, based on the monomers. In these cases, the secondary alcohols are also solvents for the monomers.

Die so erhältlichen Copolymerisate haben K-Werte von 30 bis 300, vorzugsweise 50 bis 250. Die K-Werte werden bestimmt nach H.Fikentscher in 5 %iger wäßriger Kochsalzlösung bei pH 7, 25°C und einer Polymerkonzentration von 0,1 Gew.-%.The copolymers thus obtainable have K values of 30 to 300, preferably 50 to 250. The K values are determined according to H. Fikentscher in 5% aqueous saline solution at pH 7, 25 ° C. and a polymer concentration of 0.1% by weight. -%.

Aus den oben beschriebenen Copolymerisaten erhält man durch teilweise oder vollständige Abspaltung der Formylgruppen aus dem in das Copolymerisat einpolymerisierten Monomeren I unter Bildung von Amin- bzw. Ammoniumgruppen die erfindungsgemäß zu verwendenden hydrolysierten Copolymerisate:

Figure imgb0004
The hydrolyzed copolymers to be used according to the invention are obtained from the copolymers described above by partially or completely splitting off the formyl groups from the monomer I copolymerized into the copolymer with formation of amine or ammonium groups:
Figure imgb0004

In den Formeln (II) und (III) haben die Substituenten R1 und R2 jeweils die in Formel (I) angegebene Bedeutung. In Abhängigkeit von den bei der Hydrolyse gewählten Reaktionsbedingungen erhält man entweder eine partielle oder vollständige Hydrolyse der Einheiten II. Die Hydrolyse wird so weit geführt, daß 30 bis 100, vorzugsweise 60 bis 95 %, der in das Copolymerisat einpolymerisierten Monomeren a) hydrolysiert sind. Bei der Hydrolyse von Vinylformamid-Einheiten enthaltenden Copolymerisaten kann der Hydrolysegrad beispielsweise durch Polyelektrolyttitration oder durch enzymatische Analyse der freigesetzten Ameisensäure bestimmt werden. Sofern die Copolymerisate außer den Monomeren a) und b) noch Monomere der Gruppe c) einpolymerisiert enthalten, so können auch die einpolymerisierten Monomeren c) je nach gewählter Hydrolysebedingung chemisch verändert werden, z.B. entstehen aus Vinylacetat-Einheiten Vinylalkohol-Einheiten. Der Hydrolysegrad der oben angegebenen Einheiten II beträgt vorzugsweise 60 bis 95 %.In the formulas (II) and (III), the substituents R 1 and R 2 each have the meaning given in formula (I). Depending on the reaction conditions chosen in the hydrolysis, either partial or complete hydrolysis of the units II is obtained. The hydrolysis is carried out to such an extent that 30 to 100, preferably 60 to 95%, of the monomers a) copolymerized into the copolymer are hydrolyzed. In the hydrolysis of copolymers containing vinylformamide units, the degree of hydrolysis can be determined, for example, by polyelectrolyte titration or by enzymatic analysis of the formic acid released. If the copolymers contain, in addition to the monomers a) and b), copolymerized monomers of group c), the copolymerized monomers c) can also be chemically changed depending on the hydrolysis condition chosen, for example vinyl alcohol units are formed from vinyl acetate units. The degree of hydrolysis of the units II specified above is preferably 60 to 95%.

Als Hydrolysemittel eignen sich vor allem Mineralsäuren, wie Halogenwasserstoffe, die gasförmig oder in wäßriger Lösung eingesetzt werden können. Vorzugsweise verwendet man Salzsäure, Schwefelsäure, Salpetersäure und Phosphorsäure sowie organische Säuren, wie C1- bis C5-Carbonsäuren und aliphatische oder aromatische Sulfonsäuren. Der pH-Wert bei der sauren Hydrolyse beträgt -1 bis 5, vorzugsweise 0 bis 2. Pro Formylgruppenäquivalent, das aus den einpolymerisierten Einheiten II abgespalten werden soll, benötigt man 0,05 bis 2, vorzugsweise 1 bis 1,5 Moläquivalente einer Säure.Particularly suitable hydrolysis agents are mineral acids, such as hydrogen halides, which can be used in gaseous form or in aqueous solution. Hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid and organic acids such as C 1 -C 5 -carboxylic acids and aliphatic or aromatic are preferably used Sulfonic acids. The pH in the acidic hydrolysis is -1 to 5, preferably 0 to 2. Per formyl group equivalent which is to be split off from the copolymerized units II, 0.05 to 2, preferably 1 to 1.5 molar equivalents of an acid are required.

Die Hydrolyse der einpolymerisierten Einheiten der Struktur II kann auch mit Hilfe von Basen vorgenommen werden, z.B. von Metallhydroxyden, insbesondere von Alkalimetall- und Erdalkalimetallhydroxyden. Vorzugsweise verwendet man Natriumhydroxyd oder Kaliumhydroxyd. Die Hydrolyse kann ggfs. auch in Gegenwart von Ammoniak oder Aminen durchgeführt werden.The hydrolysis of the polymerized units of structure II can also be carried out with the aid of bases, e.g. of metal hydroxides, especially of alkali metal and alkaline earth metal hydroxides. Sodium hydroxide or potassium hydroxide is preferably used. The hydrolysis can optionally also be carried out in the presence of ammonia or amines.

Besonders bewährt hat sich die Hydrolyse der Copolymerisate in wäßriger Lösung oder Suspension bei Reaktionstemperaturen von 20 bis 100°C. Sofern die nicht hydrolysierten Copolymerisate in Wasser schwer löslich sind, lösen sie sich in aller Regel mit fortschreitender Hydrolyse im Reaktionsmedium auf. Im Anschluß an eine sauer durchgeführte Hydrolyse wird das Reaktionsgemisch gegebenenfalls mit Basen, vorzugsweise Natronlauge, neutralisiert. Falls die Hydrolyse mit Basen durchgeführt worden ist, kann das Reaktionsgemisch gegebenenfalls durch Zusatz von Säuren, vorzugsweise von Salzsäure, neutralisiert werden. Die pH-Werte des Reaktionsgemisches können nach der Hydrolyse zwischen 1 und 10, vorzugsweise zwischen 3 und 8, liegen. Je nach Zusammensetzung können die hydrolysierten Copolymerisate in bestimmten pH-Bereichen schwer löslich sein. Der K-Wert der hydrolysierten Copolymerisate beträgt 10 bis 300, vorzugsweise 15 bis 200 (gemessen in 5 %iger wäßriger Kochsalzlösung bei einer Polymerkonzentration von 0,1 Gew.-%, einem pH-Wert von 1,5 und einer Temperatur von 25°C).Hydrolysis of the copolymers in aqueous solution or suspension at reaction temperatures of 20 to 100 ° C. has proven particularly useful. If the unhydrolyzed copolymers are sparingly soluble in water, they usually dissolve in the reaction medium as hydrolysis proceeds. Following an acidic hydrolysis, the reaction mixture is optionally neutralized with bases, preferably sodium hydroxide solution. If the hydrolysis has been carried out with bases, the reaction mixture can, if appropriate, be neutralized by adding acids, preferably hydrochloric acid. The pH values of the reaction mixture can be between 1 and 10, preferably between 3 and 8, after the hydrolysis. Depending on the composition, the hydrolyzed copolymers can be sparingly soluble in certain pH ranges. The K value of the hydrolyzed copolymers is 10 to 300, preferably 15 to 200 (measured in 5% aqueous sodium chloride solution at a polymer concentration of 0.1% by weight, a pH of 1.5 and a temperature of 25 ° C).

Die hydrolysierten Copolymerisate werden erfindungsgemäß bei der Herstellung von Papier verwendet. Sie werden dem Papierstoff in Mengen von 0,01 bis 5, vorzugsweise 0,1 bis 2 Gew.-%, bezogen auf trockene Fasern, zugesetzt. Die hydrolysierten Copolymerisate bewirken sowohl eine Erhöhung der Entwässerungsgeschwindigkeit und der Retention bei der Papierherstellung als auch gleichzeitig eine Erhöhung der Trocken- und Naßfestigkeit des Papiers.The hydrolyzed copolymers are used according to the invention in the manufacture of paper. They are added to the paper stock in amounts of 0.01 to 5, preferably 0.1 to 2% by weight, based on dry fibers. The hydrolyzed copolymers not only increase the rate of dewatering and retention in papermaking, but also increase the dry and wet strength of the paper.

Die K-Werte der Copolymerisate wurden nach H.Fikentscher, Cellulosechemie, Band 13, 48-64 und 71-74 (1932) in 5 %iger wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,1 Gew.-% bestimmt, wobei der K-Wert der nicht hydrolysierten Copolymerisate bei pH 7 und der der hydrolysierten Copolymerisate bei 1,5 gemessen wurde.The K values of the copolymers were determined according to H. Fikentscher, Cellulosechemie, Vol. 13, 48-64 and 71-74 (1932) in 5% aqueous saline solution at 25 ° C and a polymer concentration of 0.1% by weight. wherein the K value of the non-hydrolyzed copolymers was measured at pH 7 and that of the hydrolyzed copolymers at 1.5.

BeispieleExamples Herstellung der CopolymerisatePreparation of the copolymers Copolymerisat 1Copolymer 1

In einer Polymerisationsapparatur, die mit einem Rührer ausgestattet ist, werden 991 g destilliertes Wasser, 1,54 g 75 %ige Phosphorsäure und 1,06 g 50 %ige wäßrige Natronlauge im schwachen Stickstoffstrom auf eine Temperatur von 70°C erhitzt. Sobald diese Temperatur erreicht ist, gibt man innerhalb von 2 Stunden eine Lösung von 50 g Wasser, 39,2 g Acrylsäure und 43,6 g 50 %iger wäßriger Natronlauge, separat davon 160 g N-Vinylformamid und ebenfalls separat davon eine Lösung von 25 g Wasser und 0,05 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid, gleichmäßig zu. Nach Beendigung der Monomerzugabe dosiert man innerhalb von 1 Stunde eine Lösung von 0,15 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid in 73 g Wasser zu und rührt das Reaktionsgemisch anschließend noch 2 Stunden bei einer Temperatur von 70°C und verdünnt es dann mit 800 g Wasser. Die so erhältliche stark viskose Lösung besitzt einen Feststoffgehalt von 10,9 % und hat einen pH-Wert von 6,2. Der K-Wert des Copolymerisats beträgt 177.In a polymerization apparatus equipped with a stirrer, 991 g of distilled water, 1.54 g of 75% phosphoric acid and 1.06 g of 50% aqueous sodium hydroxide solution are heated to a temperature of 70 ° C. in a gentle stream of nitrogen. As soon as this temperature has been reached, a solution of 50 g of water, 39.2 g of acrylic acid and 43.6 g of 50% strength aqueous sodium hydroxide solution is added within 2 hours, 160 g of N-vinylformamide and a solution of 25 separately thereof g of water and 0.05 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride, evenly. After the monomer addition has ended, a solution of 0.15 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride in 73 g of water is metered in over the course of 1 hour and the reaction mixture is then stirred for a further 2 hours at a temperature of 70 ° C. and then dilute it with 800 g of water. The highly viscous solution thus obtainable has a solids content of 10.9% and a pH of 6.2. The K value of the copolymer is 177.

Hydrolyse des einpolymerisierten N-Vinylformamids von Copolymerisat 1Hydrolysis of the copolymerized N-vinylformamide of copolymer 1

500 g der oben beschriebenen wäßrigen Lösung eines Copolymerisates aus 75,4 Gew.-% Vinylformamid und 24,6 Gew.-% Natriumacrylat vom K-Wert 177 werden in einer Apparatur vorgelegt, die mit einem Rührer ausgestattet ist und mit 250 g Wasser verdünnt. Die Mischung wird zunächst bei Raumtemperatur gerührt und innerhalb von 20 min mit 80,2 g 38 %iger Salzsäure versetzt. Danach erhitzt man das Reaktiongsgemisch 7 Stunden auf eine Temperatur von 70°C, kühlt es auf Raumtemperatur ab und fügt 120 g einer 10 %igen wäßrigen Natronlauge zu. Der pH-Wert des Reaktionsgemisches beträgt danach 1,5. Um das Reaktiongsgemisch zu stabilisieren, fügt man 15 g einer 0,5 %igen wäßrigen Natriumbisulfitlösung zu. Der Hydrolysegrad des einpolymerisierten N-Vinylformamids beträgt 93 %. Die Lösung hat einen Polymergehalt von 5,8 Gew.-% (hydrolysiertes Copolymerisat 1). Der K-Wert des Polymeren beträgt 135.500 g of the above-described aqueous solution of a copolymer of 75.4% by weight of vinylformamide and 24.6% by weight of sodium acrylate with a K value of 177 are placed in an apparatus equipped with a stirrer and diluted with 250 g of water . The mixture is first stirred at room temperature and 80.2 g of 38% hydrochloric acid are added within 20 minutes. The reaction mixture is then heated to a temperature of 70 ° C. for 7 hours, cooled to room temperature and 120 g of a 10% strength aqueous sodium hydroxide solution are added. The pH of the reaction mixture is then 1.5. In order to stabilize the reaction mixture, 15 g of a 0.5% aqueous sodium bisulfite solution are added. The degree of hydrolysis of the polymerized N-vinylformamide is 93%. The solution has a polymer content of 5.8% by weight (hydrolyzed copolymer 1). The K value of the polymer is 135.

Copolymerisat 2Copolymer 2

In einer Polymerisationsapparatur werden 965,3 g Wasser, 1,34 g einer 75 %igen wäßrigen Phosphorsäure und 0,92 g einer 50 %igen wäßrigen Natronlauge im Stickstoffstrom auf einer Temperatur von 70°C erhitzt. Sobald diese Temperatur erreicht ist, fügt man jeweils innerhalb von 2 Stunden eine Mischung aus 100 g Wasser, 60 g Acrylsäure und 66,5 g 50 %iger wäßriger Natronlauge und separat davon 141,4 g N-Vinylformamid und ebenfalls separat davon eine Lösung von 0,05 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid in 25 g Wasser gleichmäßig zu. Nach Beendigung der Initiator- und Monomerzugabe fügt man innerhalb von 1 Stunde eine Lösung von 0,15 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid, gelöst in 73 g Wasser, zu und hält das Reaktionsgemisch während dieser Zeit und 2 Stunden nach Zugabe des Initiators auf einer Temperatur von 70°C. Danach fügt man 800 ml Wasser zu und erhält eine stark viskose Lösung, die einen Feststoffgehalt von 11,0 % und einen pH-Wert von 6,6 hat. Der K-Wert des Copolymerisats beträgt 172.In a polymerization apparatus, 965.3 g of water, 1.34 g of a 75% aqueous phosphoric acid and 0.92 g of a 50% aqueous sodium hydroxide solution are heated to a temperature of 70 ° C. in a stream of nitrogen. As soon as this temperature has been reached, a mixture of 100 g of water, 60 g of acrylic acid and 66.5 g of 50% strength aqueous sodium hydroxide solution and, separately therefrom, 141.4 g of N-vinylformamide and likewise separately of it are added in each case within 2 hours Evenly add 0.05 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride in 25 g of water. After the addition of initiator and monomer has ended, a solution of 0.15 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride, dissolved in 73 g of water, is added within 1 hour and the reaction mixture is kept for this time and for 2 hours after adding the initiator at a temperature of 70 ° C. Then 800 ml of water are added and a highly viscous solution is obtained which has a solids content of 11.0% and a pH of 6.6. The K value of the copolymer is 172.

Hydrolysehydrolysis

500 g der oben beschriebenen wäßrigen Lösung des Copolymerisats aus 64,1 Gew.-% N-Vinylformamid und 35,9 Gew.-% Natriumacrylat werden in einer Rührapparatur vorgelegt und durch Zugabe von 250 g Wasser verdünnt. Danach fügt man innerhalb von 20 min bei Raumtemperatur 77,2 g 38 %ige Salzsäure zu. Das Reaktionsgemisch wird dann auf eine Temperatur von 70°C erhitzt und 8 Stunden bei dieser Temperatur gerührt. Danach kühlt man es auf Raumtemperatur ab und gibt 120 g einer 10 %igen wäßrigen Natronlauge zu. Der pH-Wert des Gemisches beträgt danach 1,5. Um das Reaktionsgemisch zu stabilisieren, fügt man 15 g einer 0,5 %igen wäßrigen Natriumbisulfitlösung zu. Der Hydrolysegrad des einpolymerisierten N-Vinylformamids beträgt 95 %. Die Reaktionslösung hat einen Polymergehalt von 5,6 %. Das Copolymerisat enthält Vinylaminhydrochlorid-, Vinylformamid- und Acrylsäure-Einheiten (hydrolysiertes Copolymerisat 2). Der K-Wert des Polymeren beträgt 126.500 g of the aqueous solution of the copolymer of 64.1% by weight of N-vinylformamide and 35.9% by weight of sodium acrylate described above are placed in a stirring apparatus and diluted by adding 250 g of water. Then 77.2 g of 38% hydrochloric acid are added over the course of 20 minutes at room temperature. The reaction mixture is then heated to a temperature of 70 ° C. and stirred at this temperature for 8 hours. Then it is cooled to room temperature and 120 g of a 10% aqueous sodium hydroxide solution are added. The pH of the mixture is then 1.5. In order to stabilize the reaction mixture, 15 g of a 0.5% aqueous sodium bisulfite solution are added. The degree of hydrolysis of the polymerized N-vinylformamide is 95%. The reaction solution has a polymer content of 5.6%. The copolymer contains vinylamine hydrochloride, vinylformamide and acrylic acid units (hydrolyzed copolymer 2). The K value of the polymer is 126.

Beispiel 1example 1

Aus 50 % Fichtensulfitzellstoff und 50 % Buchensulfitzellstoff wurde eine 0,5 %ige Stoffsuspension in Wasser hergestellt. Der pH-Wert der Stoffsuspension betrug 7,0, der Mahlgrad 30° Schopper-Riegler (SR). Die Stoffsuspension wurde anschließend in 5 gleiche Teile geteilt, von denen 4 der Stoffsuspensionen mit den unter b) bis e) angegebenen Zusätzen versetzt wurden. Die 5 Stoffsuspensionen wurden anschließend zu Blättern einer Flächenmasse von 80 g/m2 in einem Rapid-Köthen-Laborblattbildner verarbeitet.A 0.5% pulp suspension in water was made from 50% spruce sulfite pulp and 50% beech sulfite pulp. The pH of the stock suspension was 7.0 and the freeness was 30 ° Schopper-Riegler (SR). The stock suspension was then divided into 5 equal parts, of which 4 of the stock suspensions were mixed with the additives indicated under b) to e). The 5 stock suspensions were then processed into sheets with a basis weight of 80 g / m 2 in a Rapid-Köthen laboratory sheet former.

Zusammensetzung der Stoffsuspensionen:

  • a) Die Stoffsuspension enthielt keine weiteren Zusätze.
  • b) Der Stoffsuspension wurde 1 %, bezogen auf die Faserstoffe, einer wäßrigen Lösung eines handelsüblichen Neutralnaßfestharzes auf Basis eines Umsetzungsproduktes von Epichlorhydrin und einem Polyamidoamin aus Diethylentriamin und Adipinsäure zugesetzt.
  • c) Der Stoffsuspension wurde 1 %, bezogen auf Faserstoff, einer wäßrigen Lösung eines Polyvinylaminhydrochlorids gemäß der US-A-2 721 140 zugesetzt.
  • d) Der Stoffsuspension wurde 1 %, bezogen auf Faserstoff, des hydrolysierten Copolymerisats 1 zugesetzt.
  • e) Der Stoffsuspension wurde 1 %, bezogen auf Faserstoff, des hydrolysierten Copolymerisats 2 zugesetzt.
Composition of the suspensions:
  • a) The stock suspension contained no further additives.
  • b) 1%, based on the fibers, of an aqueous solution of a commercially available neutral wet strength resin based on a reaction product of epichlorohydrin and a polyamidoamine of diethylene triamine and adipic acid was added to the stock suspension.
  • c) 1%, based on the fiber, of an aqueous solution of a polyvinylamine hydrochloride according to US Pat. No. 2,721,140 was added to the stock suspension.
  • d) 1%, based on the fiber, of the hydrolyzed copolymer 1 was added to the stock suspension.
  • e) 1%, based on the fiber, of the hydrolyzed copolymer 2 was added to the stock suspension.

Aus den oben beschriebenen Papierstoffsuspensionen wurden die Blätter a) bis e) hergestellt. Von den erhaltenen Blättern wurde die Weiße, die Trockenreißlänge und die Naßreißlänge gemessen. Die Ergebnisse sind in Tabelle 1 angegeben. Tabelle 1 a) b) c) d) e) Vergleich (erfindungsgemäß) Weiße (% Remissionswert) 77,9 73,5 73,4 73,1 74,0 Trockenreißlänge (m) 2354 2903 2927 3102 2895 Naßreißlänge (m) ungealtert 104 908 978 1009 956 5 min bei 110 C gealtert 106 1032 1005 1118 1040 Sheets a) to e) were produced from the paper stock suspensions described above. The whiteness, dry tearing length and wet tearing length of the sheets obtained were measured. The results are shown in Table 1. Table 1 a) b) c) d) e) comparison (according to the invention) Whiteness (% reflectance value) 77.9 73.5 73.4 73.1 74.0 Dry tear length (m) 2354 2903 2927 3102 2895 Wet tear length (m) unaged 104 908 978 1009 956 Aged at 110 C for 5 min 106 1032 1005 1118 1040

Beispiel 2Example 2

Aus 50 % Fichtensulfitzellstoff und 50 % Buchensulfitzellstoff wurde eine 0,5 %ige Stoffsuspension in Wasser hergestellt. Der pH-Wert der Stoffsuspension betrug 4,5. der Mahlgrad 30°SR. Die Stoffsuspension wurde anschließend in 5 gleiche Teile geteilt, von denen die Proben b) bis e) jeweils mit 1 %, bezogen auf trockenen Faserstoff, der unten angegebenen Zusätze versetzt wurden. Folgende Stoffsuspensionen wurden verarbeitet:

  • a) Die oben beschriebene Stoffsuspension enthielt keine weiteren Zusätze.
  • b) Der Stoffsuspension wurde eine wäßrige Lösung eines handelsüblichen Naßfestharzes auf Basis eines Umsetzungsproduktes von Harnstoff und Formaldehyd zugesetzt.
  • c) Der Stoffsuspension wurde eine wäßrige Lösung eines hydrolysierten Copolymerisats aus 70 % N-Vinylformamid und 30 % Vinylacetat, K-Wert des Polymerisats 100, Hydrolysegrad von N-Vinylformamid und Vinylacetat >90 % zugesetzt.
  • d) Der Stoffsuspension wurde das hydrolysierte Copolymerisat 1 zugesetzt.
  • e) Der Stoffsuspension wurde das hydrolysierte Copolymerisat 2 zugesetzt.
A 0.5% pulp suspension in water was made from 50% spruce sulfite pulp and 50% beech sulfite pulp. The pH of the stock suspension was 4.5. the degree of grinding 30 ° SR. The stock suspension was then divided into 5 equal parts, of which samples b) to e) were each mixed with 1%, based on dry fiber stock, of the additives specified below. The following stock suspensions were processed:
  • a) The stock suspension described above contained no further additives.
  • b) An aqueous solution of a commercially available wet strength resin based on a reaction product of urea and formaldehyde was added to the stock suspension.
  • c) An aqueous solution of a hydrolyzed copolymer of 70% N-vinylformamide and 30% vinyl acetate, K value of polymer 100, degree of hydrolysis of N-vinylformamide and vinyl acetate> 90% was added to the stock suspension.
  • d) The hydrolyzed copolymer 1 was added to the stock suspension.
  • e) The hydrolyzed copolymer 2 was added to the stock suspension.

Die oben beschriebenen Stoffsuspensionen wurden auf einem Rapid-Köthen-Gerät zu den Blättern a) bis e) verarbeitet. Die Weiße, Trockenreißlänge und die Naßfestigkeit der erhaltenen Blätter sind in Tabelle 2 angegeben Tabelle 2 a) b) c) d) e) Vergleich (erfindungsgemäß) Weiße (% Remissionswert) 80,4 77,9 75,1 75,3 75,8 Trockenreißlänge (m) 3278 3817 3950 4551 4159 Naßreißlänge (m) ungealtert 134 796 1024 1101 877 5 min bei 130 C gealtert 143 1031 1062 1196 998 The substance suspensions described above were processed on a Rapid-Köthen device to form sheets a) to e). The whiteness, dry tear length and wet strength of the sheets obtained are given in Table 2 Table 2 a) b) c) d) e) comparison (according to the invention) Whiteness (% reflectance value) 80.4 77.9 75.1 75.3 75.8 Dry tear length (m) 3278 3817 3950 4551 4159 Wet tear length (m) unaged 134 796 1024 1101 877 Aged at 130 C for 5 min 143 1031 1062 1196 998

Beispiel 3Example 3

Aus gemischtem Altpapier wurde eine 0,2 %ige Stoffsuspension in Wasser hergestellt. Der pH-Wert der Suspension betrug 7, der Mahlgrad 67°SR. Die Stoffsuspension wurde in 10 gleiche Teile geteilt. Eine Probe der Stoffsuspension blieb unverändert, während den anderen 9 Proben die unten angegebenen Zusätze zugefügt wurden. Folgende Proben lagen vor:

  • a) Die oben beschriebene Stoffsuspension enthält keine weiteren Zusätze.
  • b) Der oben beschriebenen Stoffsuspension wurden 0,1 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung eines handelsüblichen neutralen Naßfestharzes auf Basis eines Umsetzungsprodukts von Epichlorhydrin und einem Polyamidoamin aus Diethylentriamin und Adipinsäure zugesetzt.
  • c) Der oben beschriebenen Stoffsuspension wurden 0,2 %, jeweils bezogen auf die Feststoffe, des unter b) beschriebenen handelsüblichen neutralen Naßfestharzes zugesetzt.
  • d) Der oben beschriebenen Stoffsuspension wurden 0,4 %, jeweils bezogen auf die Feststoffe, des unter b) beschriebenen handelsüblichen neutralen Naßfestharzes zugesetzt.
  • e) Der oben beschriebenen Stoffsuspension wurden 0,1 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 2 zugegeben.
  • f) Die oben beschriebene Stoffsuspension wurde mit 0,2 %, jeweils bezogen auf die Feststoffe einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 2 versetzt.
  • g) Die oben beschriebene Stoffsuspension wurde mit 0,4 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 2 versetzt.
  • h) Der oben beschriebenen Stoffsuspension wurden 0,1 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 1 zugesetzt.
  • i) Der oben beschriebenen Stoffsuspension wurden 0,2 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 1 zugesetzt.
  • j) Der Stoffsuspension wurden 0,4 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 1 zugesetzt.
A 0.2% stock suspension in water was made from mixed waste paper. The pH of the suspension was 7, the freeness 67 ° SR. The stock suspension was divided into 10 equal parts. One sample of the stock suspension remained unchanged, while the other 9 samples were added with the additives listed below. The following samples were available:
  • a) The stock suspension described above contains no other additives.
  • b) 0.1%, based in each case on the solids, of a 0.1% aqueous solution of a commercial neutral wet strength resin based on a reaction product of epichlorohydrin and a polyamidoamine of diethylenetriamine and adipic acid was added to the stock suspension described above.
  • c) 0.2%, based in each case on the solids, of the commercially available neutral wet strength resin described under b) was added to the stock suspension described above.
  • d) 0.4%, based on the solids, of the commercially available neutral wet strength resin described under b) was added to the stock suspension described above.
  • e) 0.1%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 2 was added to the stock suspension described above.
  • f) 0.2%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 2 was added to the stock suspension described above.
  • g) 0.4%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 2 was added to the stock suspension described above.
  • h) 0.1%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 1 was added to the stock suspension described above.
  • i) 0.2%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 1 was added to the stock suspension described above.
  • j) 0.4%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 1 was added to the stock suspension.

Die Proben b) bis j) wurden jeweils nach einer 5minütigen Einwirkungszeit des Zusatzes in einem Laborblattbildner unter Bildung von Blättern einer Flächenmasse von 68 g/m2 entwässert. Um den Aschegehalt zu bestimmen und damit ein Maß für die Retention zu bekommen, wurden die Blätter bei Temperaturen von 900 bis 1000°C in einem Muffelofen verbrannt und der Glührückstand gravimetrisch bestimmt. Die dabei erhaltenen Ergebnisse sind in Tabelle 3 angegeben. Tabelle 3 Beispiel % Asche im Papier Zusatz in % a) Vergleichsbeispiel 5,1 0 b) Vergleichsbeispiel 8,6 0,1 c) Vergleichsbeispiel 9,0 0,2 d) Vergleichsbeispiel 10,1 0,4 e) (erfindungsgemäß) 10,2 0,1 f) (erfindungsgemäß) 11,2 0,2 g) (erfindungsgemäß) 11,6 0,4 h) (erfindungsgemäß) 10,4 0,1 i) (erfindungsgemäß) 11,1 0,2 j) (erfindungsgemäß) 11,4 0,4 Samples b) to j) were each dewatered after a 5-minute exposure time of the additive in a laboratory sheet former to form sheets with a mass per unit area of 68 g / m 2 . In order to determine the ash content and thus obtain a measure of the retention, the sheets were burned in a muffle furnace at temperatures of 900 to 1000 ° C and the residue on ignition was determined gravimetrically. The results obtained are shown in Table 3. Table 3 example % Ashes in the paper Addition in% a) Comparative example 5.1 0 b) Comparative example 8.6 0.1 c) Comparative example 9.0 0.2 d) Comparative example 10.1 0.4 e) (according to the invention) 10.2 0.1 f) (according to the invention) 11.2 0.2 g) (according to the invention) 11.6 0.4 h) (according to the invention) 10.4 0.1 i) (according to the invention) 11.1 0.2 j) (according to the invention) 11.4 0.4

Beispiel 4Example 4

Aus gemischtem Altpapier wurde eine 0,2 %ige Stoffsuspension in Wasser hergestellt. Der pH-Wert der Stoffsuspension betrug 7, der Mahlgrad 67°SR. Die Stoffsuspension wurde in 10 gleiche Teile geteilt, von denen 9 mit den unten angegebenen Zusätzen versetzt wurden:

  • a) Diese Probe enthielt keine Zusätze.
  • b) Der Stoffsuspension wurden 0,1 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung eines handelsüblichen neutralen Naßfestharzes auf Basis eines Umsetzungsprodukts von Epichlorhydrin und einem Polyamidoamin aus Diethylentriamin und Adipinsäure zugesetzt.
  • c) Der oben beschriebenen Suspension wurden 0,25 % des unter b) beschriebenen handelsüblichen Neutralnaßfestharzes zugesetzt.
  • d) Der oben beschriebenen Stoffsuspension wurden 0,4 %, jeweils bezogen auf die Feststoffe, des unter b) beschriebenen Neutralnaßfestharzes zugesetzt.
  • e) Der Stoffsuspension wurden 0,1 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 2 zugesetzt.
  • f) Der Suspension wurden 0,25 % des hydrolysierten Copolymerisats 2 zugesetzt.
  • g) Der Suspension wurden 0,4 %, jeweils bezogen auf die Feststoffe, des hydrolysierten Copolymerisats 2 zugesetzt.
  • h) Der oben beschriebenen Stoffsuspension wurden 0,1 %, jeweils bezogen auf die Feststoffe, einer 0,1 %igen wäßrigen Lösung des hydrolysierten Copolymerisats 1 zugesetzt.
  • i) Der Stoffsuspension wurden, jeweils bezogen auf die Feststoffe, 0,25 % des hydrolysierten Copolymerisats 1 zugesetzt.
  • j) Der Suspension wurden, jeweils bezogen auf die Feststoffe, 0,4 % des hydrolysierten Copolymerisats 1 zugesetzt.
A 0.2% stock suspension in water was made from mixed waste paper. The pH of the stock suspension was 7, the freeness 67 ° SR. The stock suspension was divided into 10 equal parts, 9 of which were mixed with the additives listed below:
  • a) This sample contained no additives.
  • b) 0.1%, based in each case on the solids, of a 0.1% aqueous solution of a commercial neutral wet strength resin based on a reaction product of epichlorohydrin and a polyamidoamine of diethylene triamine and adipic acid were added to the stock suspension.
  • c) 0.25% of the commercially available neutral wet strength resin described under b) was added to the suspension described above.
  • d) 0.4%, based in each case on the solids, of the neutral wet strength resin described under b) was added to the stock suspension described above.
  • e) 0.1%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 2 was added to the stock suspension.
  • f) 0.25% of the hydrolyzed copolymer 2 was added to the suspension.
  • g) 0.4%, based in each case on the solids, of the hydrolyzed copolymer 2 was added to the suspension.
  • h) 0.1%, based in each case on the solids, of a 0.1% aqueous solution of the hydrolyzed copolymer 1 was added to the stock suspension described above.
  • i) 0.25% of the hydrolyzed copolymer 1 was added to the stock suspension, based in each case on the solids.
  • j) 0.4% of the hydrolyzed copolymer 1 was added to the suspension, based in each case on the solids.

Die oben beschriebenen Proben wurden nach einer Einwirkungszeit von 5 min auf einem Schopper-Riegler-Gerät bei Raumtemperatur entwässert. Die Entwässerungszeit ist in Tabelle 4 angegeben. Tabelle 4 Beispiel Entwässerungszeit (s/700 ml) Zusatz in % a) Vergleichsbeispiel 89 0 b) Vergleichsbeispiel 68 0,1 c) Vergleichsbeispiel 60 0,25 d) Vergleichsbeispiel 50 0,4 e) (erfindungsgemäß) 57 0,1 f) (erfindungsgemäß) 21 0,25 g) (erfindungsgemäß) 10 0,4 h) (erfindungsgemäß) 46 0,1 i) (erfindungsgemäß) 31 0,25 j) (erfindungsgemäß) 21 0,4 The samples described above were dewatered after a contact time of 5 min on a Schopper-Riegler device at room temperature. The drainage time is shown in Table 4. Table 4 example Drainage time (s / 700 ml) Addition in% a) Comparative example 89 0 b) Comparative example 68 0.1 c) Comparative example 60 0.25 d) Comparative example 50 0.4 e) (according to the invention) 57 0.1 f) (according to the invention) 21 0.25 g) (according to the invention) 10th 0.4 h) (according to the invention) 46 0.1 i) (according to the invention) 31 0.25 j) (according to the invention) 21 0.4

Claims (3)

  1. Use of a copolymer which is obtainable by copolymerization of
    a) from 5 to 99 mol% of N-vinylcarboxamides of the formula
    Figure imgb0007
     where R1 and R2 are each H or C1-C6-alkyl,
    b) from 95 to 1 mol% of monoethylenically unsaturated carboxylic acids of 3 to 8 carbon atoms and/or the alkali metal, alkaline earth metal or ammonium salts thereof and, if required,
    c) up to 30 mol% of vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or a mixture thereof and, if required,
    d) up to 2 mol% of compounds which have at least two ethylenically unsaturated nonconjugated double bonds in the molecule,
    and subsequent partial or complete elimination of the
    Figure imgb0008
     groups from the monomers I polymerized in the copolymer, with formation of amino or ammonium groups, as an additive to paper stock for increasing the drainage rate and the retention in papermaking and the dry and wet strength of the paper.
  2. Use as claimed in claim 1, wherein the copolymer is obtainable by copolymerization of
    a) from 30 to 95 mol% of N-vinylformamide,
    b) from 70 to 5 mol% of acrylic acid, methacrylic acid and/ or the alkali metal, alkaline earth metal or ammonium salts thereof
    and
    c) from 0 to 30 mol% of vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole or a mixture thereof
    and subsequent hydrolysis of from 10 to 100% of the vinylformamide units polymerized in the copolymer.
  3. Use as claimed in claim 1 or 2, wherein the hydrolyzed copolymer is used in an amount of from 0.1 to 5% by weight, based on dry fibers.
EP94901873A 1992-12-07 1993-11-25 Use of hydrolysed copolymers of n-vinyl carboxylic acid amides and monoethylenically unsaturated carboxylic acids in the manufacture of paper Expired - Lifetime EP0672212B1 (en)

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DE4241117A DE4241117A1 (en) 1992-12-07 1992-12-07 Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking
PCT/EP1993/003305 WO1994013882A1 (en) 1992-12-07 1993-11-25 Use of hydrolysed copolymers of n-vinyl carboxylic acid amides and monoethylenisally unsaturated carboxylic acids in the manufacture of paper

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JP2913756B2 (en) * 1990-04-25 1999-06-28 三菱化学株式会社 How to size paper

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US8349134B2 (en) 2004-11-23 2013-01-08 Basf Se Method for producing high dry strength paper, paperboard or cardboard
WO2007104716A1 (en) * 2006-03-16 2007-09-20 Basf Se Method for producing paper, paperboard and cardboard having high dry strength
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US10626558B2 (en) 2015-08-06 2020-04-21 Solenis Technologies, L.P. Method for producing paper

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ES2088316T3 (en) 1996-08-01
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ATE139279T1 (en) 1996-06-15
DE59302953D1 (en) 1996-07-18
AU5627494A (en) 1994-07-04
WO1994013882A1 (en) 1994-06-23
CA2145286C (en) 2005-03-29
FI952739A (en) 1995-06-05
JPH08504239A (en) 1996-05-07
FI952739A0 (en) 1995-06-05
EP0672212A1 (en) 1995-09-20
CA2145286A1 (en) 1994-06-23

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